New routes to clavine-type ergot alkaloids. Part 1. First total synthesis of three natural products: (+)-setoclavine, (+)-isosetoclavine, (-)-9,10-dihydroisoseto-clavine, and structure correction of the latter

István Moldvai, Eszter Temesvári-Major, E. Gács-Baitz, Mária Incze, Gábor Dörnyei, Csaba Szántay

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The double bond in ring D of (+)-9,10-didehydro-6-methylergolin-8-one (2) was reduced selectively by catalytic hydrogenation to yield (-)-6-methylergolin-8-one (6). Grignard reaction of 6 has been performed with methylmagnesium iodide to afford two isomers (5 and 7). The main isomer having an 8α-methyl group at C8 with a C/D-trans junction (5; (-)-dihydroisosetoclavine) proved to be identical with the natural product, hence its name and structure should be corrected. As a minor isomer (7) a C/D-cis clavine derivative was also isolated which can be regarded as unnatural (+)-8α-hydroxycostaclavine. (+)-Setoclavine (8) and (+)-isosetoclavine (9) have also been prepared from 2, thus achieving the first total synthesis of these natural products. Detailed structure elecidation of 5-9 has been carried out as well.

Original languageEnglish
Pages (from-to)291-298
Number of pages8
JournalHeterocycles
Volume67
Issue number1
DOIs
Publication statusPublished - Jan 1 2006

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Ergot Alkaloids
Biological Products
Isomers
Hydrogenation
Iodides
Names
Derivatives
setoclavine

ASJC Scopus subject areas

  • Organic Chemistry

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New routes to clavine-type ergot alkaloids. Part 1. First total synthesis of three natural products : (+)-setoclavine, (+)-isosetoclavine, (-)-9,10-dihydroisoseto-clavine, and structure correction of the latter. / Moldvai, István; Temesvári-Major, Eszter; Gács-Baitz, E.; Incze, Mária; Dörnyei, Gábor; Szántay, Csaba.

In: Heterocycles, Vol. 67, No. 1, 01.01.2006, p. 291-298.

Research output: Contribution to journalArticle

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